Process of producing hydrogen sulphide



Feb. 26, 1935. R. s. BLEY 1,992,896

PROCESS OF PROD USING HYDROGEN SULPHIDE Filed'Nov. 16, 1933 Patented Feb. 26, 1935 1 it v UNITED STATES PATENT OFFICE Rudolph s. Bley, Elizabethton, Tenn., assignor to North American Rayon Corporation, New York, N. Y., a corporation of Delaware Application November 16, 1933, Serial No. 698,238

25 Claims. (01. 23-181) The present invention relates to a process of It will be noted that I have disclosed, diagramproducing hydrogen sulphide of great purity for matically, the manner in which hydrocarbons the manufacture of alkali metal sulphides which and sulphur may be heated in an autoclave, the are generally used for desulphurizing viscose passage of a stream of hydrogen sulphide to the yarns and the like. reflux condenser, the passage of the hydrogen 5 One object of my invention is to economically sulphide from the condenser, and the return of produce hydrogen sulphide on a large scale from water and intermediate decomposition products cheap waste materials such as carbohydrates and to the autoclave. Since my present invention carbohydrate-containing substances and sulcomprehends only the process for producing the hur hydrogen sulphide, I have not depicted specifical- 10 Another object of my invention is to use artily, any particular apparatus. Any suitable comficial silk waste and sulphur for the manufacture mercial autoclave and condenser may be cmof hydrogen sulphide. ployed.

A third object of this invention is to produce Silk waste, for example, and sulphur are 1-5 substantially pure, liquid hydrogen sulphide from charged into an autoclave constructed of hydrocarbohydrates and sulphur without further megen sulphide resisting material, said autoclave chanical compression. being provided with a pressure gage, safety valve I am well aware that it has, heretofore, been and suitable stirring means. Water, as set forth proposed to produce hydrogen sulphide by boiling above, may be added to the carbohydrate-sul- 20 sulphur together with alkalies under pressure, phur mass to form a thin paste which can be 2 and to develop this compound by heating hydro easily stirred. This autoclave is connected with carbons with sulphur under normal atmospheric a reflux condenser of conventional type, the same pressures. It has been found, however, that this being prov ded W th adequate cool ng means and latter process fails to yield suflicient volumes of an outlet for the hyd sulphide formed u gas, and, furthermore, that the raw materials ing the reaction. The autoclave is slowly heated 25 used in this process, in view of the aforemenby suitable means, i. e. steam coils, etc.,-under tioned poor yields of hydrogen sulphide, become Continu u Stirring to DIBSSHTES preferably Tang'- too expensive for commercial purposes. ing o 5 t0 3 atmospheres, although t is t I have found by experimentation that very be noted that the process may be carried out high yields of hydrogen sulphide are realized under lower or higher pre u If the pressures 30 when carbohydrates are heated under superatconsequently the temperatures, are raised mospheric pressures with sulphur in the presence above the liquefact n pressure of hydro S111- or absence of additional water. Any type of ma- Dbidc d the reflux condenser maintained at terial containing carbohydrates, such as saw dust, r l iv ly l w mp r ur y r n phi waste sugars, starches, molasses, cotton waste, can be produced in liquid form without additional 35 peat, plant tissues, artificial silk waste, etc., may m h n l mpr i n. The hy r sulphide be treated with sulphur under pressure to yield obtained y b p fi y y W l known hydrogen sulphide. My novel process is espea Such as abs rb s s, an cially suitable for the production of this com- Sodium u p ay be produced by caus 40 pound from rayon waste, .viz. viscose silk, cug yd sulphide to act With Sodium 40 pramrnonium silk, cellulose esters, cellulose Sulp The amounts of u phur and carethers, etc. It is to be noted that suitable catabohydrate, necessary for production of hydrolysts, such as metallic oxides, etc., may be added gen sulphide, depend upon the type of carboto the reacting mass in order to promote its dehydrate as well as the grade of sulphur used in composition and to simultaneously facilitate the the reaction. They must be individually deterunion of the final compounds obtained by demined by experimentation, although it is to be structive distillation of a carbohydrate-sulphur noted that an excess of either one of these submixture under pressure. 'The residual copper stances does not adversely affect the reaction compounds present in copper silk waste repreitself. For reasons of economy an excess of sulsents, per so, valuable catalytic agents and, thus phur or carbohydrate should be avoided. 50*

additional agents to oata e the process may It is to be noted that my process is especially be dispensed with. adapted for the production of hydrogen sulphide The attached drawing represents a diagramfrom cellulose sludge present in waste water of matic view of the manner in which my process rayon plants and paper mills. This fermented may be carried out. or still fermenting sludge contains large amounts 55 of sulphur compounds and cellulose in a finely dispersed state which readily breaks up into hydrogen sulphide on being heated under pressure in the presence of additional sulphur. Thus, the decomposition of carbohydrates by means of sulphur under pressure may be accelerated by adding thereto such cellulose sludge. Waste viscose solutions may be also used in place of cellulose sludge to speed up the formation or" hydrogen sulphide.

I wish to point out that the compounds as Well as the pressures, set forth above, are merely. illustrative and may be varied without departing from the scope and spirit of my invention. No limitations should be imposed upon my invention except as indicated in the appended claims.

I claim:

1. The process of producing hydrogen sulphide from artificial silk waste of cellulosic origin comprising heating said Waste under a superatmospheric pressure in the presence of sulphur.

2 The process of producing hydrogen sulphide from artificial silk waste of cellulosic origin comprising heating said waste under pressures of about 5 to 30 atmospheres in the presence of sulphur.

3. The process of producing hydrogen sulphide from artificial silk waste of cellulosio origin comprising heating said waste under a superatmospheric pressure in the presence of sulphur and water.

4. The process of producing hydrogen sulphide from artificial silk waste of cellulosic origin comprising heating said waste under pressures of about 5 to 30 atmospheres in the presence of sulphur and water.

5. The process of producing hydrogen sulphide from artificial silk Waste of cellulosic origin comprising heating said waste under a superatmospheric pressure in the presence of sulphur and a catalyst.

6. The process of producing hydrogen sulphide from waste viscose silk comprising heating said silk under a superatmospheric pressure in the presence of sulphur. 1

. 'I. The process of producing hydrogen sulphide from waste viscose silk comprising heating said silk waste under a superatmospheric pressure in the presence of sulphur and water.

8. The process of producing hydrogen sulphide from waste viscose silk comprising heating said silk waste under a superatmospheric pressure in the presence of sulphur, water and a catalyst.

9. The process of producing sulphide from waste cuprammonium silk comprising heating said silk waste under a superatmospherio pressure in the presence of sulphur.

10. The process of producing hydrogen sulphide from artificial silk waste of cellulosic orgin comprising heating said waste under a superatmospheric pressure in the presence of sulphur, water and a catalyst.

11. The process of producing hydrogen sulphide from artificial silk wase of cellulosic origin comprising heating said waste under a superatmospheric pressure in the presence of sulphur and an accelerator of the group consisting of cellulose sludge and waste viscose solutions.

12. The process of producing hydrogen sulphide from artificial silk waste of cellulosic origin comprising heating said waste under pressures of about 5 to 30 atmospheres in the presence of sulphur and a catalyst.

13. The process of producing hydrogen sulphide from artificial silk waste of cellulosic origin comprising heating said waste under pressures of about 5 to 30 atmospheres in the presence of sulphur, water and a catalyst.

14. The process of producing hydrogen sulphide from artificial silk waste of cellulosic origin comprising heating said waste under pressures of about 5 to 30 atmospheres in the presence of sulphur and an accelerator of the group consisting of cellulose sludge and waste viscose solutions.

15. The process of producing hydrogen sulphide from Waste viscose silk comprising heating said silk under a superatmospheric pressure in the presence of sulphur and a catalyst.

16. The process of producing hydrogen sulphide from waste viscose silk comprising heating said silk under a superatmospheric pressure in the presence of sulphur and an accelerator of the group consisting of cellulose sludge and waste viscose solutions.

17. The process of producing hydrogen sulphide from waste viscose silk comprising heating said silk under pressures of about 5 to 30 atmospheres in the presence of sulphur.

18. The process of producing hydrogen sulphide from waste viscose silk comprising heating said silk under pressures of about 5 to 30 atmospheres in the presence of sulphur and a catalyst.

19. The process of producing hydrogen sulphide from waste viscose silk comprising heating said silk under pressures of about 5 to 30 atmospheres in the presence of sulphur and an accelerator of the group consisting of cellulose sludge and waste viscose solutions.

20. The process of producing hydrogen sulphide from waste ouprammonium cellulose silk comprising heating said silk under a superatmospheric pressure in the presence of sulphur and water.

21. The process of producing hydrogen sulphide comprising heating waste cuprammonium cellulose silk containing residual copper compounds under a superatmospheric pressure in the presence of sulphur.

22. The process of producing hydrogen sulphide comprising heating waste cuprammonium cellulose silk containing residual copper compounds under pressures of about 5 to 30 atmospheres in the presence of sulphur.

23. The process of producing hydrogen sulphide from waste cuprammoniurn silk comprising heating said silk under a superatmospheric pressure in the presence of sulphur and an accelerator of the group consisting of cellulose sludge and waste viscose solutions.

24. The process of producing hydrogen sulphide from waste cuprammonium cellulose silk comprising heating said silk under pressures of about 5 to 30 atmospheres in the presence of sulphur.

25. The process of producing hydrogen sulphide from waste cuprammonium cellulose silk com prising heating said silk under pressures of about 5 to 30 atmospheres in the presence of sulphur and an accelerator of the group consisting of cellulose sludge and waste viscose solutions.

RUDOLPH S. BLEY. 

